1,3,5-triazinediones

ABSTRACT

Herbicidal 1,3,5-triazinediones of the formula: WHEREIN X1, X2, R1, R2 and R3 are as hereinafter defined. Certain of these triazinediones are useful for the selective control of weeds in crops, e.g. wheat and soybeans. Exemplary of the class of compounds are 1-methyl-2-cyclopentyl6-methylthio-s-triazine-2,4(1H,3H)-dione and 1-methyl-3cyclohexyl-6-methylthio-s-triazine-2,4(1H,3H)-dione, which are useful for the selective control of weeds in wheat and soybeans, respectively.

United States Patent [191 Fuchs et al.

1 1 1,3,5-TRIAZINEDIONES [75] Inventors: Julius Jakob Fuchs, Wilmington;

Kang- Lin, Newark, both of Del.

[73] Assignee: E. l. du Pont de Nemours and Company, Wilmington, Del.

[22] Filed: Apr. 5, 1973 121] App]. N0.: 348,322

Related US. Application Data [63] Continuation-impart of Ser. No. 325,358, Jan. 22,

1973, abandoned.

Primary E.\'aminer.lohn M. Ford I 1-methy1-2-cyclopentyl-6-methylthio-s-triazine- 1 2,4(1H,3H)-dione [451 Mar. 25, 1975 [57] ABSTRACT Herbicidal 1,3,5-triazinediones of the formula:

wherein X,, X R,, R and R are as hereinafter defined. Certain of these triazinediones are useful for the selective control of weeds in crops, e.g. wheat and soybeans.

Exemplary of the class of compounds are and 1-methy1-3-cyclohexyl-6-methylthio-s-triazine- 2,4(1H,3H)-dione, which are useful for the selective control of weeds in wheat and soybeans, respectively.

. 11 Claims, N0 Drawings l ,3, -TRI AZINEDIONES CROSS-REFERENCE TO RELATED APPLICATION This application is a continuation-impart of our copending U.S. Pat. application. Ser. No. 325,358, filed Jan. 22, 1973, now abandoned.

BACKGROUND OF THE INVENTION Neumayer et al., Pesticides, Chemical Week, Apr. 12 and 26, 1969, lists several commercial and experimental s-triazine herbicides. Among these are prometone and prometryne, which have the structural formulae:

where R represents hydrogen or certain organic radicals, the R"s represent certain organic radicals and the X s represent oxygen or sulfur. These compounds are disclosed as being useful as selective herbicides.

The compounds of the above-mentioned copending application are intermediates in the preparation of the novel and highly active class of herbicides of the present invention.

SUMMARY OF THE INVENTION This invention is a class of novel herbicidally active compounds of the formula:

wherein R, is alkyl of 3 through 8 carbon atoms, cycloalkyl of 3 through 8 carbon atoms, methylcyclopenty], methylcyclohexyl, dimethylcyclohexyl, trimethylcyclohexyl, tetramethylcyclohexyl, cycloalkylalkyl of 4 through 7 carbon atoms, alkenyl of 3 through 4 carbon atoms, alkynyl of 3 through 4 carbon atoms, benzyl or where Y is hydrogen, halogen, alkyl of I through 4 carbon atoms, nitro, alkoxy of I through 4 carbon atoms,

alkylthio of 1 through 4 carbon atoms, cyano, or I trifluoromethyl, Z is hydrogen, halogen, methyl, ethyl, nitro, alkoxy of 1 through 4 carbon atoms, or alkylthio of I through 4 carbon atoms, and Q is hydrogen, halo- 5 gen, or methyl; R is alkyl of I through 4 carbon atoms; R, is SR, or OR,, where- R, is alkyl of I through 6 carbon atoms, cycloalkyl Preferred Compounds Certain of the compounds of Formula I are preferred because of their higher herbicidal activity and their ease of synthesis. These include compounds of Formula I where:

R, is alkyl of 3 through 6 carbon atoms or cycloalkyl of 5 through 8 carbon atoms;

R is methyl;

R is SR, or 0R R is alkyl of I through 6 carbon atoms or alkenyl of 3 through 4 carbon atoms; and

X, and X are oxygen.

More preferred because of their highest herbicidal activity and selectivity are those compounds of Formula I where:

R, is alkyl of 3 through 4 carbon atoms or cycloalkyl of 5 through 7 carbon atoms;

R, is methyl;

R3 IS SCI-I3, SC2H5, OCH3 Or X, and X, are oxygen.

Preferred herbicidal compounds of the above formula include:

l methyl-3-cyclopentyl-6-methylthio-s-triazine-2,4- (lH,3I-I) dione I l-methyl-3-cyclohexyl-6-methylthio-s triazine-2,4- (1H,3H) dione 1-methyl-3-isopropyl-6-methylthio-s-triazine-2,4- (lH,3H)-dione l-methyl-3 -tert-butyl-6-methylthio-s-triazine-Z,4- (lH,3H)-dione l-methyl-3-cyclopentyl--ethylthio-s-triazine-2,4- (lH,3H)-dione l-methyl-3-cyclohexyl-6-cthylthio-s-triazine-2,4- (lH,3H)-dione l-methyl-3-cyclopentyl-o-methoxy-s-triazine-2,4- (lH,3H)-dione l-methyl-3-cyclopentyl-6-ethoxy-s-triazine- Synthesis of the Compounds The compounds of Formula I where X X oxygen can be prepared by the process illustrated by the following equations:

R R and R are as previously defined;

X is oxygen or sulfur;

M is an alkali metal. and

R is hydrogen or alkyl of 1 through 4 carbon atoms The synthesis of l-thioallophanimidates and l,3-dithioallophanimidates from thiopseudourea [equation 1)] are performed analogous to a procedure given in Organic Synthesis 42, 87 (1962), which describes the preparation of methyl 4-phenyl-3-thioallophanimidate (1-phenyl-2-thio-4-methylisobiuret).

The reaction products of equation (1 are allowed to react at about O45C and atmospheric pressure in an inert organic solvent, e.g., methylene chloride, with one equivalent of a chloroformate or a chlorothiolformate in the presence of one equivalent of an acid acceptor such as tricthylamine. trimethylamine or dimethylaniline [equation 2)]. After the completion of the reaction, the methylene chloride solution is washed with water, dried, and the solvent evaporated to give alkoxycarbonylthioallophanimidates, alkylthiolcarbonylthioallophanimidates, alkoxycarbonylallophanimidates and alky,lthiol carbonylallophanimidates.

The reaction products of equation(2) are also obtained by reacting the pseudourea or thiopseudourea first with a chloroformate or a chlorothiolformate as in equation la), and then reacting the reaction products olequation la) with an isocyanate as in equation (2a).

The reaction products of equation (2) are then refluxed for a short time with an alkali metal alkoxide or hydroxide such as sodium or potassium methoxide or hydroxide in methanol to effect cyclization [equation 3)]. The solvent is evaporated under vacuum; the residue is washed with ether or dissolved in water and acidified. Acidification of the aqueous solution usually precipitates the desired s-triazinedione as an essentially pure solid. If the desired compound does not precipitate upon acidification, it is extracted into methylene chloride. The solvent is then evaporated and the dried residue is recrystallized. The essentially pure alkali metal salt (corresponding to the alkali metal in the alkoxide or hydroxide) is obtained by washing the residue with ether and filtering the resulting solid. The same alkali metal salts are also obtained by dissolving the striazinediones in methanol containing one equivalent of alkali metal alkoxideor hydroxide such as sodium methoxide or hydroxide followed by evaporation of methanol. The alkali metal salts of s-tria zinediones react with alkyl halides, sulfates, or tosylates to provide the l-alkyl analogs of the this invention [equation 4)]. Both components are refluxed at about l53C in an appropriate inert organic solvent such as tetrahydrofuran, dimethylformamide, or acetonitrile for 5-10 hours. The solvent is evaporated and the residue dissolved in methylene chloride. The methylene chloride solution is washed with water, dried and evaporated to provide the l-alkyl analogs of this invention in an essentially pure state.

The compounds of Formula I can also be prepared by the process illustrated by the following equations:

X: R: i

zine-2,4( lH,3H)-dithiones of the present invention can 5 6 also be prepared by the process illustrated by the fol- The actual percentages that can be realized with a lowing equation: particular compound of Formula I will depend upon its physical properties. v (7) s The manner of making and using such herbicidal for- 1 l mulations is described in numerous patents. See, for ex- N ample, Luckenbaugh us. Pat. No. 3,309,192, Lawti J l L U.S. Pat. No. 3,235,357, Todd U.S. Pat. No. 2,655,445, N R3 R8 Hamm et al. U.S. Pat. No. 2,863,752, Scherer et al. l U.S. Pat. No. 3,079,244, Gysin et al. U.S. Pat. No.

10 2,891,855, and Barrous U.S. Pat. No. 2,642,354.

Examples of suitable formulations of compounds of A s-tria2ine-2,4( lH,3H)-dione is reacted with phosthe present invention include the following: phorus pentasulfide at about 25125C in a solvent xa such as pyridine to produce the desired s-triazine-4- E mple l thio-2,4(lH,3H)-dione. The solvent is removed by S l (7 b. I h evaporation and the residue recrystallized in a solvent l l U SUCh as benzene. l-met hyl-3-cyclohexyl-6-methylthio- 37 Formulation and Use of the Compounds s-triazinc-2. lH.3H)-dione ethylene glycol monobutvl ether 35 The compounds of the present invention are useful methanol 9 herbicides. Certain of these compounds can be used for ate 19 the control of weeds in crops, such as wheat and soybeans, without injury to such crops.

The compounds can be applied preemergence as a The ingredients are combined and stirred to produce directed postemergence treatment or in certain specific :lsolutlon Much Can be extended water for spray cases as an overall postemergence treatment. Application rates range from A to 10 kilograms/hectare. EXAMPLE 2 Method and rate of application depend upon such factors as crop, soil type, climatic condition, and weed wettable powder: 7 (by weight) population. Uniform distribution of the compounds is I h 13 I I 6 1th if These compounds may also be combined with other diatomaceous earth 71.5 herbicides such as linuron, terbutryn, diuron, terbacil, i"l""ll f ff f ow viscosity methyl cellulose 2 I and paraquat to control a broader spectrum of weeds. The compounds of Formula I can be formulated in the various ways which are conventional for herbicides The ingredients are thoroughly blended and passed of Similar P y P p Useful folmulatlons' through a hammer mill to produce particles essentially clude wettable and soluble powders, oil suspensions all below 100 microns and solunQnsi aqueous dlsperslollsi dusts, granulesi F The herbicidal activity of compounds of this invenletb l hlgh S g P P Q Broadly speakmgi tion was discovered in a greenhouse test. In this test, these tormulatioiis consist essentially ofabout l to 99/1 40 Seeds of crabgrass (Dim-my, spp), barnyardgruss by wclgm l mfltenul "l l (Eclziiioclilou crus-galli'j, wild oats (Alelluftlllld), Casleast one compound ol Formula I in a herbicidally et- Sia tom, morningglory (momma 5mm mustard lective amount) and at least one of (a) about ().l to [M Spp.)a radish (Rap/mum XML), murigold y' 20% weight oi-su rf ce active agent and (b) about5 4S Sp), dock (Ru/mu. Nix/m, and nutscdgc tuhurs O to 99/1 by weight ol essentially biologically inert solid poms Sp) were phmtcd in d growth medium and or liquid diluent. More specifically, the various types of treated pmemergence with the chemical dissolved in a lOlllllllilllttllS Wlll generally containthcse ingredients in nomphywtoxic solvent. Treated plums and Controls Ihc lollowmg approximate P P were maintained in a greenhouse for l6 days, then all species were compared to controls and visually rated for responses to treatment. A qualitative (type of plant p by wgigln response) rating was made. The letter C indicates Hsrbicids Dims"! Surfflclm chlorosis; and G indicates growth retardation. The

ts H- tt*n' I Womble Powders 35 90 O m 74 I 10 letter S indicates albinism. The symbol nd cates Oil Suspensions or 5 that the compound was not tested on the indicated 35 94 I m plant. A qualitative rating on a scale of O to 10 means Aqueous Dispersions 50 4t) 89 l l0 35 o 99 i) 5 maximum effect, e.g., complete kill in case of chlorosis. gni nu lcs amt: Pellets l 35 99 0 15 Results obtained in this test for some highly active comigi treiigti k cumpflsilions 90 99 0 0 3 gfunds of this invention are given in the following ta PREEMERGENCE Barn- Morti- Kg/ Crabyard Wild Nlll iiig Miis- Marilitietarii grass grass oats siidgii Cassia glory tiiril ltiidisli gold l)(l('.k l-niiil.hyl-3-oyclopeiityl-lS-iiiiithyltliin-ii-ti'iaziiie- 2.2 100 ii(! Hit, lit? 10(1 lot; lot. Hit? lot; mt! 2,4(ll|,3|l) tli0llt!. 0.41 mi: st, Sit! 0 Hit! llitl ior: iiii: int: .1"!

l iititliylJJ-cyt:lriliiixyl-tl-irtlioxy-s-ti'iiiziiii 2. 2 lot; 10(1 Hit. It. lliti ltitf Hit. lt tl Hill lot. 2,4|l,3ll)- li0iie. 0.44 in: 100 8t! 0 mi: 10 m l iiii lllf ioi l-iiii:thyl-ii-tm-liiiI.yl-fi-iiiethylLhiii-ieti'iaziiiiill lit) fit, st: ii' lot? Hit. ii tt Int? ,Hl iitt 2,4(1ll,3l|)-(ll0nie. 2.2 so iii: no ii iriii mi: mi: lllt! iii:

PREEM ERG ENC E Continued Barn- Morn- Kg/ Crabyard Wild Nuting Mus- Marihectare grass grass oats sedge Cassia glory tard Radish gold Dock 1-methy1-3-(p-chlorophenyl)-6-metl1ylthio-s- 2. 2 7C 7 (2 4C 10C 10C 100 0C 10C 10C triazine-2,4(lH,3H)-dione. 0. 44 1C 4 C 2C 0 10C 10C 10C 80 2C 3C 1-mcthy1-3-scc-butyl-G-methylthio-a-triazinu- 11 9C 100 JC 0 10C 10C 10( 10( 100 JC 2,4(1II,3H)-dione. 2. 2 0U 00 8C 0 10C 10C 10( 10C 10C 10C l-methyl-3-cyelohexyl-G-methylthio-s-triazine- 11 {)0 10(3 10C 20 10C 10C 10(! 10( 10C 10C 2,4(11I,3II)-di0ne. 2.2 at) 10C 100 1C 10C 10C 10( 10C 10C 10C l-methyl-3-(m-chloropl1cnyl)-6-mrLhylthio-s- 11 0( 10(3 10(1 0 10C 10C 10( 10( 10C 10C triazine-2,4(1II,3H)-di0i1e. 2. 2 00 10C 10C 0 10C 10(1 100 10( 10( 0C 1-methyl-3-(0-tlu0rophenyD-G-methylthitrs- 11 90 J0 JO 0 10C 10C 10( 10(7 100 0C tnazine-ifl(1H,3H)-di0ne. 2. 2 2G 46 (i0 0 10C 10C 10C M 0(3 0(1 1-methyl-3-(2-methy1cycl0hexyl)-6 methyltl1i0-s- 2. 2 0C 10C 00 1 C 10C 10C 10( 10( 10C 10( triazine-2,4(lI-I,3H)-dione. 0. 44 70 0C 8C 0 10C 10C 10C 10C 100 JC 1-methyl-3-cycloheptyl-fi-methylthio-s-triazine- 2. 2 10C 10C 10C 20 10C 10C 10C 10C 10( 10C 2,4(1H,3H)-di0ne. 0. 44 10C 100 0C 0 10C 10C 10C 10C 10C 10(, 1-methy1-3-cyclooctyl-(S-methylthio-s-ttiazine- 2. 2 00 10C 10C 0 60 10C 10C 10C 10( 8( 2,4(1H,3H) di0ne. 0.4-1 8C 8C 8C 0 3C 10C 10C 80 6G G 1-ethyl-B-cyclohexyl-fi-methylthio-s-triazinc- 2. 2 C 10C 10C 0 1 C 10C 10C 10C 10C 10C 2,4(1H,3I-I)-dione. 0. 44 9C 4U 5C 0 0 10C 10C 100 6G 0G 1-methyl-3-(3-methylcyclohexyl)-6-metl1ylthio-s- 2. 2 10C 10C 90 5C ()0 10C 10C 10C 10( .10 triazine-2,4(1H,3H)-dione. 0. 44 JC 00 8C 0 5C 10C 10C 10C 10( 0C 1-methy13-ne0pentyl-tS-methylthios-triazine- 2. 2 7G 00 JC 56 10C 10C 10C 10( 10C 10( 2,4(1H,3H)-dione. 0.44 3G 5G 2C 10C 0C 10C 20 RC 1-1nethyl-3-(p-chlorophenyl)-6-methoxy-s- 11 10C 100 0C 50 10C 10C 10C 10C 10( 10 U triazine-2,4(1H,3H)-dione. 2. 2 10C 4C 88 20 10C 0C 0G 0G 8C 100 l-methyl-3-isopr0pyl-6-methylthio-s-triazine- 11 9C 100 0C 20 10C 10C 10C 10( 10C 10C 2,4(1H,3H)-dione. 2.2 8C 10C 70 0 10C 10C 10C 10C 10C 100 this test are detailed in the following table:

kg/ wild downy hectare wheat oats brome cheat 1.10 2C lOC IUC 10C 0.55 2C 10C 10C IOC 0.27 0 10C lOC 9C In another test, seeds of wheat, wild oats, downy brome and cheat were planted in soil contained in greenhouse pots. After one week, the young plants were sprayed with l-methyl-3-cyclopentyl-6- methylthio-s-triazine-2,4(lH,3H)-dione in a nonphytoxic solvent with a wetting agent and a humectant. The pots were maintained in a greenhouse for three weeks. The species were compared to controls and vi-' sually rated for response to treatment as described above. The results obtained in this test are detailed in the following table:

kg/ Wild downy hectare wheat oats brome cheat 0.55 lC 7C IOC l0C 0.27 0 0 2C 6C 0.13 0 0 0 1C 0.07 0 0 0 0 Thus, it can be seen that l-methyl-3-cyclopentyl6- methylthio-s-triazine-Z,4(lH,3H)-dione is very effective a selective herbicide for use in wheat crops both preemergence and post-emergence.

In another test, seeds of crabgrass, barnyardgrass, wild oats, johnsongrass (Sorghum lzalepense), dallasgrass (Paspalum dilimrum), giant foxtail (Setaria fuberii), bluegrass (Poa plate/Isis), ripgut (Bromus rigrlus),

goosegrass (Eleusine indica), mustard, dock, pigweed' (Amaranthus retroflexus), nutsedgc, curly indigo (Aesclzynomene virginica), yellow rocket (Barbarea vulgarus), teaweed (Sida spinosa), jimsonweed (Datum srramonium), moringglory and soybean were planted in containers of a Fallsington sandy loam soil and treated preemergence with l-methyl-3-cyclohexyl-6- methylthio-s-triazine-2,4( ll-l,3H)-dione in a nonphytotoxic solvent. The treated containers were placed in a greenhouse and maintained for four weeks. The species were compared to controls and visually rated for response to treatment as described above. The results obtained in this test are detailed in the following table:

KgJhectare KgJhcctare (Jral) grass 8C Dock 10C 10C Barnyard grass... ,A 10( 8(3 ligwomL. 10( 10(? Wild oats"... 10( 2t) Nutsodgu l) 0 Johnson grass... 7C 3(l (.urlvy indigo 100 50 Dallas grass c r 10(1 .10 Yellowrockut 100 5G Giant foxtail 0C 50 Teawuedwn. c 10( 10C Bluegrass 100 8C .limsonweed 8C 10( Ripgut... 10C 10C Morning glory. 10C 10(- Goose grass. 100 5G Soybean 1C 0 Mustard 10C 10C EXAMPLE 3 l -methyl-3-isopropyl-6-methylthio-s-triazine- 2,4( lH,3H)-dione To a solution of 69.5 parts of 2-methyl-2- thiopseudourea sulfate and 47 parts of methyl chloroformate in 1000 parts of water at C is added dropwise, 56.9 parts of potassium hydroxide in 200 parts of water. The reaction mixture is stirred at room temperature for 3 hours and then extracted with methylene chloride. The methylene chloride extract is dried and the solvent evaporated on a rotary evaporator to give 45 parts of methyl N-( l-amino-l-methylthiomethylenel-carbamate, m.p. 7277C.

Seventy-four parts of the above compound and 47 parts of isopropyl isocyanate in 300 parts methylene chloride are stirred overnight. The solvent is evaporated on a rotary evaporator to give 113.6 parts of methyl 4-isopropyl-N-methoxycarbonyl-1-thioallophanimidate. m.p. 129-l32C.

One hundred parts of the above compound is refluxed for 1 hour with 27 parts of sodium methoxide in 200 parts methanol. The methanol is stripped on a rotary evaporator and the residue dissolved in 200 parts of water. The aqueous solution is neutralized with hydrochloric acid, the solid filtered and dried to yield 55 parts of 3-isopropyl-6-methylthio-s-triazine- 2,4( lH,3H)-dione. m.p. 188-190C.

To a solution of 32 parts of sodium methoxide in 400 parts of methanol is added 132 parts of 3-isopropyl-6- methylthio-s-triazine-Z,4( l H.3H )-dione. The solution is evaporated under vacuum, and the white solid is triturated with methylene chloride and filtered to give 1 parts of sodium 3-isopropyl-6-methylthio-s-triazine- 24( lH.3H)-dione, m.p. above 300C.

Eighty parts of sodium 3-isopropyl-6-methylthio-striazine-2,4(1H,3H)-dione and 49 parts of methyl iodide are refluxed overnight in 700 parts of acetonitrile. The solvent is evaporated and the residue dissolved in methylene chloride. The methylene chloride solution is washed with water, dried, and evaporated to afford after recrystallization from chlorobutane/hexane 54 parts of 1-methyl-3-isopropyl-6-methylthio-s-triazine- 2,4-( 1 H,3H)-dione, m.p. 7477C.

EXAMPLE 4 l-Methyl-3'phenyl-6-methylthio-s-triazine- 2,4( 1H,3H )-dione Twenty-six parts of sodium 3-phenyl-6-methylthio-striazine-2,4( 1H,3H)-dione (prepared in a manner similar to that described in Example 1 for preparation of sodium 3-isopropyl-6-methylthio-s-trlazine- 2.4( lH,3H)-dione. except substituting phenyl isocyanate for the isopropyl isocyanate) and 16 parts of methyl iodide are refluxed in 200 parts of acetonitrile. The solvent is evaporated and the residue dissolved in methylene chloride. The methylene chloride solution is washed with water, dried, and evaporated to afford 18 parts of 1-methyl-3-phenyl-6-methylthio-s-triazine-2,4- (lH.3H)-dione. m.p. 232.5233C.

EXAMPLE 5 l--Methyl-3-tert-butyl-o-methylthio-s-triazine- 2,4( lH.3H )-dione To a solution of 278 parts of 2-methyl-2- thiopseudourea sulfate in 2000 parts of 50% aqueous methanol at 0C is added dropwise 176 parts of 50% sodium hydroxide, followed by 180 parts tert-butyl isocyanatc in 400 parts tetrahydrofuran. The solution is partially evaporated on a rotary evaporator and filtered to yield, after drying, 180 parts of methyl 4-tert-butyll-thioallophanimidate, m.p. 102104C.

To a solution of 113.4 parts of the above compound and parts of triethylamine in 1,000 parts methylene chloride at 0C is added dropwise 66 parts methyl chlorothiolformate in parts of methylene chloride. The solution is stirred overnight, washed once with water, dried and evaporated to provide 76 parts methyl 4-tert-butyl-N-methylthiolcarbonyl-l-thioallophanimidate, m.p. 102l05C.

Fifty parts of the above compound is refluxed for one hour with 30 parts of sodium methoxide in 500 parts of methanol. The reaction mixture is then cooled and the methanol is stripped on a rotary evaporator. The residue is washed with ether to provide 30 parts sodium 3- tert-butyl-6-methylthio-s-triazine-2,4( 1H,3H )-dione.

Twenty-four parts of sodium 3-tert-butyl-6- methylthio-s-triazine-Z,4(1H,3H)-dione and 15.5 parts of methyl iodide are refluxed overnight in 200 parts of acetonitrile. The solvent is evaporated and the residue dissolved in methylene chloride. The methylene chloride solution is washed with water, dried, and evaporated to afford after recrystallization from chlorobutane 15 parts of l-methyl-3-tert-butyl-6-methylthio-striazine-2,4( lH,3H)-dione, m.p. 138l40C.

EXAMPLE 6 l-Methyl-3-cyclohexyl-6-methylthio-s-triazine-2,4- (lH,3H)-dione To 84 parts of,methyl N-( l-amino-l-methylthiomethylene) -carbamate in 500 parts of methylene chloride is added 71 parts of cyclohexyl isocyanate and a catalyst amount of dibutyltin dilaurate. The solution is refluxed for 3 hours and cooled. To it is added 31 parts of sodium methoxide in 300 parts of methanol. The solution is refluxed for one hour and the solvent evaporated on a rotary evaporator. The residue is triturated with ether to give 71 parts of sodium 3-cyclohexyl-6- methylthio-striazine-2,4( lH,3H)-dione, m.p. above 300C. t

A suspension of 26 parts of the above compound in 200 parts of acetonitrile containing 16 parts of methyl iodide is refluxed overnight. The solvent is evaporated on a rotary evaporator. Water and methylene chloride are added to the residue. The methylene chloride layer is dried and evaporated on a rotary evaporator to give after trituration with pentane 19 parts of l-methyl-3- cyclohexyl-6-methylthio-s-triazine-2,4( l H,3H)-dione, m.p. l35137C.

The productis also prepared by using dimethyl sulfate as the alkylating agent. To 439 parts of 3- cyclohexyl-6-methylthio-s-triazine-2,4( l H,3H )-dione sodium salt in 2,500 parts of water of 25C and pH 9-9.5 is added dropwise over one hour 284 parts of dimethyl sulfate. The solid formed is filtered and dried to give 324 parts of crude l-methyl-3-cyclohexyl-6- methylthio-s-triazine-2.4( l H,3H )-dio'ne, m.p. l34l38C.

EXAMPLE 7 l-Methyl-3-cyclopentyl-6-methylthio-s-triazine- 2,4(lH,3H)-dione Fifty parts of sodium 3-cyclopentyl-6-methylthio-striaZine-2,4( lH,3H)-dione (prepared in a manner-simi lar to that described in Example 1 for preparation of sodium 3-isopropyl-6-methylthio-s-triazine- 2.4( l H.3H )-dione, but substituting cyclopentyl isocyanate for the isopropyl isocyanate) and 31 parts of methyl iodide are refluxed in 400 parts of acetonitrile. The solvent is evaporated and the residue is dissolved in methylene chloride. The methylene chloride solution is washed with water, dried, evaporated, and the residue is recrystallized in a chlorobutane/hexane mixture to afford 24 parts of l'methyl-3-cyclopentyl-6- methylthio-striazine-2.4( l H,3H)-dione, m.p. 8()-83C.

EXAMPLES To 130 parts of the above compound in 200 ml of,

chlorophenyl-isocyanate. The reaction mass isstirred overnight. The solvent is evaporated and the residue refluxed for 3 hours in 100 parts of methanol containing 54 parts of sodium methoxide. The mixture is evaporated to dryness to give 300 parts of sodium 3-(pchlorophenyl )-6-methoxy-s-triazine-2.4( lH.3H dione.

To 70 parts of the triazinedione sodium salt in 250 parts of dimethylformamide is added 54 parts of methyl p-toluenesulfonate. The mixture is stirred overnight-at room temperature, and the solvent is evaporated under vacuum. The residue is triturated with a W: sodium carbonate solution, and the resulting solid is recrystallized from acetonitrile to give 30 parts of pure 1- methyl-3-(p-chlorophenyl)-6-mcthoxy-s-triazine- 2,4(lH,3H)-dione, m.p. l85l87C.

EXAMPLE 9 The s-triazinediones listed in the following table can be prepared by the procedures of Examples 3-8 by substituting the listed Z-substituted thiopseudoureas and pseudoureas for Z-methylpseudourea and Z-methyl-Z- thiopseudourea, by employing other isocyanatcs and by replacing the methyl p-toluenesulfonate and methyl ioof methyl N-( l-ammol -methoxy-methylene)- carbamate, m.p. 3639.5C. dide with the listed alkylating agents:

Thiopscudourca or Pseudourea lsocyannte Alkylating Agent s lriazinediones l-ethylpseudourea isopropyl methyl p-toluenel-ml3ll1yl-3-lSUpll)pyl-(\-UlhtIXy-S-' isocyanate sulfonale triazine-2.4( lH,3H(-dione N,, [.4900 Z-methylpseudourea m-fluorophenyl l-methy|-3-(m-lluorophenyl)-( methoxyisocyanate do. s-triazine-ZAl l H.3H)-dionc. m.p.

l56l58( m-chlorophenyl l-methyl-3(m-chlorophenyl )-(imethoxydo. isocyanate do s-triazinc2,4( l H.3H )-dione. m.p.

l86l,88C Z-ethylpseudourea cyclohexyl l-methyl-3-cyclohexyl-6-ethoxy-sisocyanate do. triazine-2.4( lH.3H)-dione, N 1.56M) 2-methyl-Z-thiosec-butyl methyl iodide l-methyl-3-sec-butyl-6-mcthylthio-spseudourea isocyanate triazine-2.4(l H. 3H)-dione. N,,'-'-"= 1.5382 l-methylcyelopentyl l-methyl-3-(l-methylcyclopentyl)-6-methy|- do. isocyanate do. thio-s-triazine-ZAU H. 3H)-dione. m.p. 8486C. cycloheptyl l-methyl-3-cycloheptyl-6-methylthio-sdo. isocyanate do. triazine-2,4( lH,3H)-dione, m.p. 98-l0lC Z-methylcyclol-methyl-3-(Z-methylcyclohexyl)-6-methyl do. hexyl isocynate do. thio-s-triazine-2,4( lH,3H)-dione, m.p.

98-l0OC 2.4.6-trimethylcyclol-methyl-3-(2,4,6-trimethylcyclohexyl)-6-methyldo. hexyl isocyunate do. thio-s-triazine-2,4( lH,3H )-dione 3,5-dimethylcyclol-mcthyl-3-(3.5-dimethylcyclohexyl)-6-methyldo. hexyl isocyanate do. thio-s-triazine-2,4( lH.3H)-dione. N 1.5400

2.3.5,-tetramethylcyclol-methyl-3-(2.3,5.-tetramethylcyclohexyl)-6- do. hexyl isocyanate do. methylthio-s-triazine-2,4( lH.3H)-dione 3.4-dimethycyclohexyl l-methyl-3-( 3.4-dimethylcyclohexyl Hi-methylthiodo. isocyanate do. s-triaz|ne-2,4(1H,3H)-dione. m.p. 8587 2,5-dimethylcyclohexyl l-methyl-3-(2,5-dimcthylcyclohcxyl)-6-methylthiodo. isocyanate do. s-triazine-2,4-( lH,3H )-dione, N,,- l.5382 Z-methyl-Z 'clooctyl methyl iodide l-methyl-3-cyclooctyl-o-mcthylthio-sthiopseudourea isocyanate triazine 2,4( lH.3HJ-dione, m.p. XS-945C.

3-methylcyclol-methyl-3-(B-melhylcyclohexyl)-6-methgvldo. hexyl isocyanate do. thio-s-triaiine-ZAt'lH.3HJ-dionc, m.p. 5-97C.

neopentyl l-methyl-3-neopentyl6-methylthio-s-triazinedo. isocyanate do. 2,4( lH,3H)-d|one, m.p. 99l()3C.

isopropyl n-hutyl iodide l-butyl-3-isopropyl-6-methylthio-s-triazinedo. isocyanate 2,4( lH.3H)-dione, N .5 I43 p-ehlorophenyl n-propyl iodide l-propyl-3-(p-chlorophenylj-(u-mcthyldo. isocyanate thio-s-triazinc-2.4( lH,3H )-dione,

m.p. Mil-150C isopropyl l-propyl-B-isopro yl-6-methylthio-sdo. isocyanatc do. triazme-2.4( lH. H)-dione. m.p.

9296C methyl iodide l-methyl-3-isopropyl-6-methylthiodo. do. s-triazine-2,4( lH,3H)-dione, N

L525? m-trifluoromethyll-methyl-Ii-l m-trifluoromethylphenyl do. phenyl isocyanatc do. fi-methylthio-s-triaZine-Zfil lH.3H)-

dione. m.p. 7(J.5-73(.' m-nitrophenyl l-mcthyl-3-(m-nitl ophenyl)6-methyl do. isocyanate do. thio-s'triazine'2.4( IH.3H l-dionc,

m.p. 23924()C henzyl isocyanate l-methyl3-benzyl-6-methylthio-sdo. do. triazine-2.4( lH.3H)-dionc. m.p.

l'lnopseutlourcu or Pscudourca lsocyanate Alkylating Agent. s-Triitzinedioncs Z-methyl-Z-thio- 2,3-dimethylcyclomethyl iodide l-methyl-3(2,3dimethylcyclohexylj-b-methylpseudourea hexyl isocyanate thio-s-triazine-2,4-( lH,3H)-dione.N,, .5382

2.4-dimethylcyclol-methyl-3(2,4-dimethylcyclohexyl)-6-methyldo. hexyl isocyanate do. thio-s-triazine-2,4-( lH.3H )-dione.N,,'- l.5332

cyclopentyl ethyl iodide l-ethyl-3-cyclopentyl-o-methylthio-s-triazincdo. 2,4-( lH,3Hl-dionc. m.p. (all-70C.

n-propyl iodide l-n-propyl-3-cyclopentyl-o-methylthio-s-trido. do. azine-1,4( lH.3H)-dione. N 1.5444 n-butyl iodide l-n-but\'l-3-c \'c|o -tent\l-o-methrlthio-s-trido. do. azine-l-l-t lH.3 )-dione. ME" 1.5420

p-ethylphenyl methyl iodide l-methyl-3-(p-ethylphenyl )-o-mcth \'lthio-sdo. isocyanate triazine-ZA-t lH,3H )-dione, m.p. '195-l9b 3,4-xylyl l-methyl-3-(3,4-xylyl)-6-methylthios-trido. isocyanate do. azine-2,4-( lH,3H)-dione, m.p. 206

4-chloro-3-tril-methyl-3-(4-chloro-3'trifluoromethylphenyl)- do. fluoromethyldo. 6-methylthio-s-triazine-2.4-( lH,3H)-dione,

phenyl isocyanate m.p. 2072l2 4-chloro-3-fluorol-methyl-3-(4-chloro-3-trifluor0phenyl )-6- do. phenyl isocyanate do. methylthio-s-triazine-2,4-( lH,3H)-d1one,

Z-methyl-Z-thiop -methoxyphenyl methyl iodide m.p. l80-l82 l-methyl-3-( p-methoxyphe nyl j-o-methylthio-spseudourea lsocyanate triazine-2,4'( lH,3H)-dione, m.p. l9620lC.

p-ethoxyphenyl l-methyl-3-(p-ethoxyphenyl)-6-methylthio-sdo. isocyanate do. triazine-2,4-( lH,3H)-dione, m.p. l96.5l99C. 2,4-dimethylphenyl l-methyl-3-( 2,4-dimethoxyphenyl )-6-methylthiodo. isoeyanate do. s-triazine-2,4-( lH,3H)-dione, m.p. l57l59C.

m-iodophenyl l-methyl-3-(m-iodophenyl)-6-methylthio-s-trido. isocyanate do. azine-2,4-(lH,3H)-dione. m.p. 168-174C.

p-cyanophenyl l-methyl-3-(p-cyanophenyl)-6-methylthio-s-trido. isocyanate do. azine-2,4-( lH,3l-l)-dione, m.p. 2l22l4C. Z-methylcyclopentyl methyl p-toluene l-methyl-3-cyclopentyl-6-methoxy-s-triazine-2,4-

pseudourea lsocyanate sulfonate (lH,3H)-dione. m.p. 9697C.

EXAMPLE l0 1-methyl-3-cyclohexyl-6-methoxy-4-thio-s-triazmel-Methyl-3-cyclohexyl-6-methylthio-s-triazine-4-thio- 2,4( l H.3H)-dione 7.8 Parts of phosphorus pentasulfide is added to a mixture of 25.5 parts of l-methyl-3-cyclohexyl-6- methylthio-s-triazine-Z,4( lH,3H)-dione (prepared by the process described in Example 6) in 60 parts of pyridine. The mixture is refluxed for 12 hours. After cooling, parts of said pyridine is removed by evaporation at reduced pressure, and 100 parts of benzene is added to the residue. The mixture is heated to reflux, and the supernatant is decanted. The residue is mixed with 100 parts of fresh benzene and heated to reflux. The supernatant is again decanted. The procedure is repeated a third time with lOO parts of benzene. The supernatants are combined and concentrated at reduced pressure, and the resulting crude product is extracted with fresh benzene. The benzene solution is concentrated and passed into a chromatographic column containing 700 parts of activity Ill neutral alumina. Fresh benzene is passed through the column, and the eluate from the first 1250 parts of benzene is concentrated to dryness to give 18.6 parts of l-methyl-3-cyclohexyl-6- mcthylthio-s-triazine-4-thio-2,4( lH,3H )-dionc, m.p. l57l59C.

The following s-triazine-4-thio-2.4( lH,3H )-dioncs can be prepared in a similar manner by using the appropriate reactants:

l-mcthyl-3-cyclohexyl-6-methylthio-4-thio-striazine-2.4( lH,3H)-dione. m.p. l58l59C.

l-mcthyl-3-cyclopentyl-6-methylthio-4-thio-striazine2,4( lH,3H )-dione, m.p. 99l02C.

l-methyl-3-isopropyl-6-methylthio-4-thio-s-triazine- 2,4( lH,3H )-dione l -mcthyl-3-tert-hutyl-o-methylthio-4-thio-s-triazine- 2,4( l H.3H l-dione l-methyl-3-cyclopentyl-6-methoxy-4-thio-s-triazine- 2,4( l H,3H )-dione 30 2,4( l H,3H)-dione 1-methyl-3 -cyc[opentyl-6-ethylthio-4-thio-s-triazine- 2,4( lH,3H )-dione EXAM PLE ll 1-Methyl-3-cyclopentyl-6-methylthio-2-thio-s-triazine- 2,4( lH,3H )-dione The above named compound can be made by the following process:

40 Twenty-one parts of methyl N-methyl-4-cyclopentyll-thioallophanimidate and 20 parts of triethylamine in 200 parts of methylene chloride are added dropwise to a solution of 12 parts of thiophosgene in 200 parts of methylene chloride at 0C. The reaction is kept at 0C for one hour and refluxed for 10 hours. The solution is washed with water and dried. The solvent is evaporated to give a residue which is recrystallized from chlorobutane to give l-methyl 3-cyclopentyl-6-methylthio-2- thio-s-triazine-2,4( 1 H,3H)-dione.

The following thio-s-triazine-2,4( l H,-3H)-diones and 2,4( lH,3H)-dione l-methyl-3-cyclopentyl-6-methylthio-s-triazine-2,4- (lH,3H)-dithione l-methyl-3-cyclohexyl-6-methylthio-s-triazine-2,4 (lH,3H )-dithione l-methyl-3-isopropyl-6-methylthio-s-triazine-Z,4- (lH,3H)-dithione l-methyl-3-tert-butyl-6-methylthio-s-triazine-2,4- (lH,3H )-dithione l-methyl-3-cyclopentyl-o-methoxy-s-triazine-2,4- (lH,3H )-dithione l-methyl-3-cyclohexyl-o-ethoxy-s-triazine-2-,4- (lH,3H )-dithione.

We claim:

1. A compound of the formula wherein R is alkyl of 3through 8 carbon atoms, cycloalkyl of 3 through 8 carbon atoms, methylcyclopentyl, methylcyclohexyl, dimethylcyclohexyl, trimethylcyclohexyl, tetramethylcyclohexyl, cycloalkylalkyl of 4 through 7 carbon atoms, alkenyl of 3 through 4 carbon atoms, alkynyl of 3 through 4 carbon atoms, benzyl, or

' 20 through 4 carbon atoms, alkynyl of 3 through 4 carbon atoms, or benzyl, and

X and X are oxygen or sulfur.

2. A compound of claim 1 wherein R is alkyl of 3 through 8 carbon atoms, cycloalkyl of 3 through 8 carbon atoms, cycloalkylalkyl of 4 through 7 carbon atoms, alkenyl or 3 through 4 carbon atoms, alkynyl of 3 through 4 carbon atoms, benzyl, or

where Y is hydrogen, halogen, alkyl of 1 through 4 carbon atoms, nitro, alkoxy of I through 4 carbon atoms, alkylthio of 1 through 4 carbon atoms, cyano, or

trifluoromethyl, and

Z is hydrogen, halogen, methyl, ethyl, nitro, alkoxy of 1 through 4 carbon atoms, or alkylthio of 1 through 4 carbon atoms; and

Q is hydrogen, halogen, or methyl.

3. A compound of claim 1 wherein R is alkyl of 3 through 6 carbon atoms or cycloalkyl of 5 through 7 carbon atoms;

R is methyl; 3

R is SR, or OR, where R, is alkyl of 1 through 6 carbon atoms or alkenyl of 3 through 4 carbon atoms; and

X and X are oxygen.

4. The compound ofclaim l which is l-methyl-3-tertbutyl-6-methylthio-s-triazine-Z,4( ll-l,3H)-dione.

5. The compound of claim 1 which is l-methyl-3- isopropyl-6-methylthio-s-triazine-2,4( lH,3H )-dione.

6. The compound of claim 1 which is l-methyl-3- cyclohexyl-o-methylthio-s-triazine-2,4( lH,3H )-dione.

7. The compound of claim l which is l-methyl-3- cyclopentyl-o-methylthio-s-triazine-Z,4( lH,3H )-dione.

8. The compound of claim 1 which is l-methyl-3- cyclohexy1-6-ethylthio-s-triazine-Z,4(lH,3H)-dione.

9. The compound of claim 1 which is l-methyl-3- cyclopentyl-6-ethylthio-s-triazine-Z,4( l H,3H )-dione.

10. The compound of claim 1 which is l-methyl-3- cyclopentyl-6-methoxy-s-triazine-2,4( lH.3H)-dione.

11. The compound of claim 1 which is l-methyl-3- 

1. A COMPOUND OF THE FORMULA
 2. A compound of claim 1 wherein R1 is alkyl of 3 through 8 carbon atoms, cycloalkyl of 3 through 8 carbon atoms, cycloalkylalkyl of 4 through 7 carbon atoms, alkenyl or 3 through 4 carbon atoms, alkynyl of 3 through 4 carbon atoms, benzyl, or
 3. A compound of claim 1 wherein R1 is alkyl of 3 through 6 carbon atoms or cycloalkyl of 5 through 7 carbon atoms; R2 is methyl; R3 is SR4 or OR4 where R4 is alkyl of 1 through 6 carbon atoms or alkenyl of 3 through 4 carbon atoms; and X and X2 are oxygen.
 4. The compound of claim 1 which is 1-methyl-3-tert-butyl-6-methylthio-s-triazine-2,4(1H,3H)-dione.
 5. The compound of claim 1 which is 1-methyl-3-isopropyl-6-methylthio-s-triazine-2,4(1H,3H)-dione.
 6. The compound of claim 1 which is 1-methyl-3-cyclohexyl-6-methylthio-s-triazine-2,4(1H,3H)-dione.
 7. The compound of claim 1 which is 1-methyl-3-cyclopentyl-6-methylthio-s-triazine-2,4(1H,3H)-dione.
 8. The compound of claim 1 which is 1-methyl-3-cyclohexyl-6-ethylthio-s-triazine-2,4(1H,3H)-dione.
 9. The compound of claim 1 which is 1-methyl-3-cyclopentyl-6-ethylthio-s-triazine-2,4(1H,3H)-dione.
 10. The compound of claim 1 which is 1-methyl-3-cyclopentyl-6-methoxy-s-triazine-2,4(1H,3H)-dione.
 11. The compound of claim 1 which is 1-metHyl-3-cyclopentyl-6-ethoxy-s-triazine-2,4(1H,3H)-dione. 